Michael-type addition products of nitroparaffins

ABSTRACT

This invention concerns Beta -(2-carbonylhydrocarbyloxyethyl) nitroalkane products derived from the addition of nitroparaffins containing 10 to 24 carbon atoms to vinyl-type reactants. These addition products generally are useful as plasticizers for uncured polyvinyl-type polymers.

United States Patent [191 Crawford et al.

[ Dec. 2, 1975 [54] MICHAEL-TYPE ADDITION PRODUCTS OF NITROPARAFFINS [75] Inventors: Wheller C. Crawford, Fishkill;

William P. Doyle, Lagrangeville; John A. Patterson, Fishkill, all of NY.

[73] Assignee: Texaco Inc., New York, NY.

[22] Filed: June 29, 1972 [21] Appl. No.: 267,320

Related US. Application Data [62] Division of Ser. No. 836,940, June 26, 1969,

abandoned.

[52] US. Cl 260/404; 260/31.2 R; 260/31.8 G; 260/3l.8 W; 260/32.4; 260/290 P; 260/297 R; 260/347.3; 260/404.5; 260/464; 260/478; 260/561 R; 260/590; 260/593 R; 260/607 A [51] Int. Cl. C07C 69/00; C08K 5/09 [58] Field of Search 260/404, 404.5

[56] References Cited UNITED STATES PATENTS 2,998,437 8/1961 Benton 260/404.5

FOREIGN PATENTS OR APPLICATIONS 906,868 9/1962 United Kingdom 260/404.5

OTHER PUBLICATIONS Reinheckel et al., 1, Monatsh. Chem. 98(5), 1944-1953 (1967).

Reinheckel et al., ll, Chem. Ber. 95, 876 (1962). Finkbeiner et al., Journ. Amer. Chem. Soc. 85 (1963), pp. 616-622.

Wakamatsu et al., Journ. Org. Chem., May 1962, pp. 1609-1611.

Primary Examiner-Ethel G. Love Attorney, Agent, or Firm-Thomas H. Whaley; Carl G. Ries; Bernard Marlowe [57] ABSTRACT This invention concerns B-( 2-carbonylhydrocarbyloxyethyl) nitro alkane products derived from the addition of nitroparaffins containing 10 to 24 carbon atoms to vinyl-type reactants. These addition products generally are useful as plasticizers for uncured polyvinyltype polymers.

1 Claim, N0 Drawings MICHAEL-TYPE ADDITION PRODUCTS OF NITROPARAFFINS This is a division of application Ser. No. 836,940 filed June 26, 1969, now abandoned.

This invention concerns base catalyzed Michael-type additions of nitroparaffins to vinyl-type reactants to form adducts.

More particularly, this invention relates to base catalyzed addition of nitroparaffins, containing 3 or more carbon atoms to vinyl-type reactants, under anhydrous conditions in a substantially aprotic environment to produce adducts in near quantitative yields. These adductsare generally useful as bifunctional reactants and, in the case of some of higher molecular weight nitroparaffin adducts, are useful as plasticizers for vinyl polymers.

Nitroparaffins containing a methenyl, methylene or methyl group contiguous to the nitro group add to'vinyl-type compounds in Michael-type additions. The adducts are usually generically catagorized as beta substituted ethylated products but the adducts with acrylonitrile also are known as cyanoethylated adducts. The usual conditions required for this type of addition are alkaline catalysts and an aqueous or alcoholic solvent environment. When the nitroparaffin reactant contains 6 or less carbon atoms, the process is rapid and pro duces quantitative yields at temperatures under 100C. and at atmospheric pressures. Unfortunately, when the secondary nitroparaffins containing 10 or more carbon atoms are reacted under the same basic alcoholic or aqueous conditions, the addition takes place to a much lesser extent and can only be pushed to quantitative yields when costly pressurized systems are employed. The drop in yield is not apparently due simply to solubility differences since methanol solubilizes .these higher molecular weight secondary nitroparaffins and the reaction mixture is homogenous.

Inasmuch as the higher molecular weight nitroparaffins, containing 10 to carbon atoms, are potentially available in large quantities from the nitration of paraffins (particularly the vapor-liquid phase nitration of C to C paraffins) it is especially desirable to provide a process which could be utilized to produce useful bifunctional addition products. Particularly useful would be an addition process which could utilize both primary and secondary nitroparaffins as reactants, either in the form of discrete compounds or their unresolved mixtures, either free from inert solvent or containing large quantities of paraffmic starting materials. Ideally, this type of process would proceed readily at moderate temperatures and atmospheric pressures and would produce the products in near quantitative yields in an easily isolable form. A process combining these attributes would represent a significant advance in the art."

It is an object of this invention, among others. to provide a novel process for preparing the base catalyzed addition products of nitroparaffins and vinyl-tape reactants, in improved yield.

It is another object of this invention to provide reaction conditions wherein secondary nitroparaffins containing 10 or more carbon atoms can be added to vinyltype compounds to produce the Michael-type addition products.

Another object of this invention is the preparation of heretofore unprepared adducts derived from the 2 above-described reaction of vinyl-type compounds with nitroparaffins.

Other more specific objects are the preparation of novel adducts from the reaction of higher molecular weight nitroparaffins with vinyl-type compounds such as acrylonitriles, alkyl acrylates, vinyl sulfones and ketones and the like which are useful as plasticizers for vinyl polymers.

Additional objects will suggest themselves to those skilled in the art after a further reading of this disclosure.

The above objects are achieved by the novel process described below.

In practice, at least one nitroparaffin reactant is admixed with at least one equi-molar quantities of at least one vinyl-type reactant in the presence of a catalytic quantity of at least one strongly alkaline material, in an anhydrous, substantially aprotic environment, to form a reaction mixture. Then the reaction mixture is heated at a temperature and for a time until addition of the Iii-- troparaffin to the vinyltype compound takes place and the addition product is prepared. The product can be further reacted in situ or isolated using standard proce dures of the art.

In the favored practice, at least one nitroparaffin re-- actant containing 10 or more carbon atoms is admixed with a slight excess of at least one vinyl-type reactant in the presence of a catalytic quantity of at least one strongly alkaline material, in an anhydrous. substantially aprotic environment, to form a reaction mixture. Then the reaction mixture is heated between 20 and 150C. until substantial addition of the nitroparaffin to the vinyl-type reactant takes place and the addition product is prepared. The reaction mixture is neutralized with acidic material and the product separated from the solvent mixture.

In the preferred practice, a nitroparaffin mixture comprising G to C secondary nitroparaffins is admixed with an excess of a vinyl-type reactant in the presence of a catalytic amount of an alkaline material selected from alkali metal and alkaline earth metal hydroxides and alkoxides and the like, in an anhydrous, substantially aprotic environment to form a reaction mixture. Thenthe reaction mixture is heated between about 50 and 80C. until the addition of nitroparaffm to vinyl-type reactant takes place and the addition product is produced. The reaction mixture is neutralized and treated as before.

In order to further aid in the understanding of the inventive process. the following additional disclosure is provided.

A: Nitroparaffin reactants The nitroparaffins which-can be used as reactants comprise the primary and secondary nitrated paraffins containing from 3 to 40 and higher carbon atoms and which have a methe- 3 chael-type addition using the processes described in the prior art.

The secondary nitroparaffins which are utilized as reactants are principally mixtures having the nitro groups randomly distributed along the hydrocarbon chain. Lower molecular weight nitroparaffins, though less preferred, can also be used as reactants in the inventive process. Illustrative nitroparaffin reactants include ni tropropanes, nitrobutanes, nitropentanes. nitrohexanes. nitrocyclohexanes, nitroheptanes, nitrooctanes, nitrononanes, nitrodecanes, nitroundecanes, nitrododecanes. nitrotridecanes, nitrotetradecanes, nitropentadecanes, as well as the higher homologues and mixtures of any or all of these nitroparaffins.

B: Vinyl-type reactants The vinyl-type reactants which can be employed contain at least 3 carbon atoms and at least one reactive vinyl grouping. The favored vinyl-type reactants are included within the structure:

wherein A is selected from the group consisting of -CN. SO CH CH COOR-, CONH COR R and R are selected from the group consisting of hydrogen and methyl and R is selected from the group consisting of alkyl radicals containing 1 to 12 carbon atoms, cycloalkyl radicals containing from 6 to 8 carbon atoms, aryl radicals containing from 6 to 10 carbon atoms.

Illustrative vinyl-type reactants include nitriles such as acrylonitrile. crotonitrile and methacrylonitrile, acrylates such as methyl. ethyl, hexyl, cyclohexyl, ally], methallyl. Z-ethylhexyl, phenyl, beta-hydroxyethyl, betacyanoethyl, furfuryl. dimethylaminoethyl, furfuryl, diethylaminoethyl and pentachlorophenyl acrylates, diacrylates such as ethylene and propylene diacrylates. vinylpyridines such as 2vinylpyridines and 4-vinylpyridines. vinyl ketones. such as methyl, ethyl and phenyl vinyl ketones, etc.

The preferred vinyl-type reactants are compounds referred to as acrylate-type structures. These include acrylonitrile. alkyl acrylates, alkyl methacrylates, and the dialkylaminoalkyl methacrylates, containing preferably from 4 to 36 carbon atoms. Illustrative alkyl acrylates include methyl acrylate, ethyl acrylate, stearyl acrylate, and allyl acrylate. Illustrative methacrylates include n-butyl methacrylate, n-octyl methacrylate. lauryl methacrylate and the like. Illustrative dialkylaminoalkyl methacrylates include diethylaminoethyl methacrylate and dipropylaminoethyl methacrylate and the like, while typical dialkylamino acrylates include diethylaminoethyl acrylate and dipropylaminoethyl acrylate among others.

C: Addition As used throughout this disclosure, this is the generic term used to describe the derivatives which result from the Michael-type of addition of nitroparaffin reactants to the vinyl-type reactants.

D: Anhydrous aprotic solvent environment The environment used in the inventive process is substantially anhydrous since both the catalyst and solvent used are substantially free from water. The aprotic sovlents are dipolar solvents having a dielectric constant F in excess of 15 at 25C. and cannot donate protons for hydrogen bonding to any appreciable extent. These solvents are resistant to decomposition during the alkaline reaction conditions that prevail during the addition. Illustrative aprotic solvents which may be used include the alkyl sulfoxides such as dimethyl sulfoxide and diisopropyl sulfoxide. tetramethylene sulfone, alkylformamides such as N.N-dimethylformamide, alkyl phosphoramides such as trimethyl phosphoramide and hexamethyl phosphoramide, and thioureas such as N,N- dimethyl thiourea and tetramethyl thiourea.

The preferred aprotic solvents are the alkyl sulfoxides such as dimethyl sulfoxide, the alkylformamides such as N,N-dimethylformamide and the alkyl phosphoramides such as hexamethyl phosphoramide. These solvents are preferred since they are especially good solvents for both the nitroparaffin and vinyl-type reactants and when used as a reaction environment, produce the addition products in good yield. While the volume of aprotic solvent used is not ordinarily critical, it is preferred that sufficient solvent be present to provide a liquid reaction mixture.

E: Strongly alkaline material This is the generic term used to describe the basic catalysts required for the addition in aprotic solvent. These include liquid ammonia, alkali metal alkoxides, and hydroxides and the alkaline earth hydroxides, as well as other materials that are strongly alkaline in aprotic solvents. Illustrative of these are potassium fluoride and quaternary ammonium hydroxides. The preferred catalysts, because of efficacy. are those selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. These catalysts are used in concentrations ranging from about 0.75 to 20% by weight or higher based upon the weight of the nitroparaffin reactant used. This concentration range is herein referred to throughout this application as a catalytic quantity (or amount) of catalyst. The preferred concentration of catalyst which ordinarily will suffice for good yields varies between about 1 to 13% by weight based upon the nitroparaffin reactant.

F: Reaction Conditions 1. Reaction Temperatures The reaction temperatures necessary for the addition to take place are relatively flexible. For example, temperatures between about 20 and 150C. can be employed to form the ad ducts of this invention. However, the best results have been obtained when a narrower temperature range is employed. This preferred temperature range is between about 50 and C.

2. Reaction Pressures Atmospheric pressures are generally preferred since they are sufficient to produce the desired addition products in good yield without the need for more costly pressurized equipment. However, if desired, superatmospheric pressures can be employed, particularly where anhydrous ammonia or a comparable gaseous material is used in the reaction.

3. Reaction Time The reaction time required for significant formation of the addition products is a vari- 4. Molar Ratios Ordinarily, near equimolar ratios of nitroparaft'm to vinyl-type reactant are employed. However, the favored procedure is to use a 0.1 molar excess of vinyl-type reactant to nitroparaffm. Preferably the ratio of vinyl-type reactant to nitroparaffm reactant will vary from 1.1:1 to 2:1 when the secondary nitroparaffins containing to 24 carbon atoms are reacted with a vinyl-type reactant such as acrylonitrile, alkyl acrylate or alkyl methacrylate.

5. Additional Inert Solvent While ordinarily the addition is conducted in a substantially anhydrous environment comprising one or more aprotic solvents the presence of additional inert solvent is not detrimental. For example, where the preferred nitroparaffin reactants (the mixtures of secondary nitroparaffins containing 10 to 24 carbon atoms) are obtained from vaporliquid phase nitration they are accompanied with from 50 to 85% by weight or more of unreacted paraffins. In these instances it is convenient to conduct the addition in the presence of these paraffinic, or comparable, inert solvents. This, in fact, can readily be done and is one of the salient advantages of the inventive process.

6. Isolation and Purification of Addition Product After the addition is complete the reaction mixture is cooled and neutralized with an acidic reagent. When an alkaline earth metal hydroxide is used as catalyst it is convenient to neutralize with carbon dioxide and re move the insoluble carbonate which precipitates. When the alkali metal hydroxides are used as catalyst a mineral acid, such as hydrochloric or sulfuric, is used to neutralize the reaction mixture. After the neutralization is complete, the method of isolation depends upon the solvent environment used. Where only aprotic solvent is present, the reaction mixture is cooled, neutralized and sufficient water added to form two phases. The organic phase which contains the addition product is separated under vacuum and the product isolated. In either case, the adduct products can be further purified by vacuum distillation or by percolation through materials such as alumina or silica gel.

7. Order of Addition of Reactants There is no critical order of addition of the reactants. However, consistently high yields are obtained when the nitroparaffin, aprotic solvent and strongly alkaline catalyst are charged into the reaction vessel and the vinyl-type reactant is added dropwise to the stirred reaction mixture. The rate of addition is regulated to maintain the temperature between about 50 and 80C.

G: Cyanoethylated Nitroparaffins As indicated earlier when the nitroparaffins are added to acrylonitrile the addition products are cyanoethylated products, formed as shown below:

Rs Base wherein R R and R are selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 12 carbon atoms, straight chain or branched chain.

When the addition products contain at least 13 carbon atoms they are useful as plasticizers for vinyl-type polymers such as polyvinyl chloride and polyvinyl acetate. When used for this purpose the formulations are prepared by mixing from 15 to 70 parts by weight of the addition product with from 90 to 120 parts by weight of the polyvinyl polymer and l to 10 parts by weight of at least one thermal stabilizer. The mixture of ingredients is placed in a shearing-type mixer at room temperature, preferably below F. and later subjected to vacuum to remove any air intrapped during mixing. To obtain optimum physical properties it is necessary to expose the mixture of ingredients to elevated temperatures. preferably between 300-375F. The resultant polymers have improved low temperature flexibility. good tensile modulus and improved resistance to extraction with hexane and soap and water compared to polymers containing nitroparaffins plasticizers.

In order to describe the novel process in the greatest possible detail, the following illustrative examples are submitted.

EXAMPLE 1 Preparation of Cyanoethylated Derivatives of a Mixture of Secondary Nitroparaffins Containing from 10 to 14 Carbon Atoms Using the Inventive Process To an appropriate reaction vessel equipped with thermometer heating and stirring means are added 500 parts by weight of a mixture of C to C secondary nitroparaffins (derived in this instance, by the vapor-liquid phase nitration of the corresponding paraffms with nitrogen dioxide), 180 parts by weight of acrylonitrile, 4 parts by weight of powdered sodium hydroxide and 1200 parts by weight of N, N-dimethylformamide The reaction mixture is heated with stirring to 70C. for 22 hours. At the end of this time the reaction mixture is allowed to cool to room temperature and the stirred mixture is treated with 5 parts by weight of concentrated hydrochloric acid to neutralize it and 1200 parts by weight of water. Two phases are produced. the upper organic phase containing virtually uncontaminated cyanoethylated product and the bottom aqueous phase containing the N, N-dimethylformamide solvent. After separation the upper layer is analyzed by infrared and gas chromatography which establish that a 96% yield of B-(Z-cyanoethyUC (i-C 1, nitroparaffin product is obtained based upon nitroparaffin starting material. As can be seen from the following example, this is a substantial increase over what is normally obtained using the prior art process.

EXAMPLE 2 Preparation of Cyanoethylated Derivatives of a Mixture of Secondary Nitroparaffins Containing From 10 to 14 Carbon Atoms Using the Process of the Prior Art The procedure of Example 1 is followed exactly using the same reactants, catalyst and quantities of reactants. Only the solvents employed differ. In this run a 700 by weight portion of methanol is substituted for N,N- dimethylformamide used in Example 1. After heating for 24 hours at 65C., the reaction mixture is neutralized as before after cooling. However, in order to separate the addition product it is necessary to strip off all of the methanol and unreacted nitroparaffin. Prior to stripping, infrared and gas chromatography establish that a yield of 67.3% of the mixed product is obtained based upon starting nitroparaffin. This is 30% less than is obtained in the preceding example using the inventive process. Repeat runs established that this difference is a real difference and demonstrates the superiority of the inventive process.

EXAMPLE 3 Preparation of Cyanoethylated Derivatives of Mixed Secondary Nitroparaffins in the Presence of Paraffinic Contaminant To an appropriate reaction vessel equipped with thermometer heating and stirring means are added 100 parts by weight of a mixture of secondary C C nitroparaffins and secondary C ,.,-C H paraffins (comprising The second reaction mixture which comprises 22 parts by weight of C m-C 14 secondary nitroparaffins, 14 parts by weight of 2-vinylpyridine-N-oxide. 5 parts by weight of powdered potassium hydroxide 200 parts by weight of N,N-dimethylformamide produces (after work-up) oz-(Z-[Z-pyridyl-N-oxide] ethyl) CUFCH ni troparaffins product.

The third reaction mixture is identical to the second reaction mixture except that 4-vinylpyridine-N-oxide is lo the vinyl reactant. After work-up the product is a-(Z- 25 parts by wet ht of the nitro araffins and 75 arts by weight of paraff ms) 9.5 parts b weight of acrylgnitrile, l4'pyndyl-N'oxlde] ethyl) nitroparaffin prod 4 parts by weight of powdered sodium hydroxide and 150 parts by weight of N-N-dimethylformamide. The EXAMPLE 8 reaction mixture is heated with stirring to 70C. for 6 H hours. At the end of this time the reaction mixture is clmoethylanon of Nltrododecane allowed to cool to room temperature and the stirred, To a reaction vessel such as is described in the previcooled mixture treated with 10 parts by weight of conous examples is added 44 parts by weight of nitrodocentrated hydrochloric acid, 100 parts by weight of decane, 13 parts by weight of acrylonitrile and 1 part of water and 100 parts by weight of petroleum ether. Two 70 powdered potassium hydroxide in 100 parts by weight phases separate and the upper organic phase is re- 7 of N,N-dimethylformamide. The reaction mixture is moved, dried. and stripped under vacuum to give 99 heated with stirring at 75C. for 24 hours. At the end of parts by weight of a product which infrared and gas this time the reaction mixture is allowed to cool to chromatographic analysis confirm to be 67.2 parts by room temperature and the stirred, cooled mixture is weight of paraffin and 32.9 parts by weight of cyanotreated with 18 parts by weight of concentrated hydroethylated C C nitroparaffins. No unreacted nitro- T chloric acid, 75 parts by weight of water and 75 parts paraffin is observed. by weight of petroleum ether. The organic phase which separates is removed, dried and stripped under vacuum EXAMPLE 4 to yield 53 parts by weight of a product which elemen- Preparation of a (2-Propionylethyl) C o-C 20 tal infrared and gas chromatographic analysis establish Nitroparaffins to be ,B-(Z-cyanoethyl) nitrododecane.

Using the procedure described in Example 1. a EXAMPLE 9 stirred reaction mixture com risin 110 arts b 'wei ht OfCHFCH Secondary nitropalzuffini 45 5 3, Weight Preparation of a Michael-Type Addition Product of of ethyl vinyl ketone, 0.9 parts by weight of powdered Nltrododecane Wlth Methyl Acrylate potassium hydroxide and 200 parts by weight of N,N- Using the previously described inventive procedure, dimethylformamide is heated for 26 hours at 73C., 44 parts by weight of nitrododecane. 22 parts by weight cooled to room temperature and acidified with 5 parts of methyl acrylate and 2 parts by weight of powdered by weight of concentrated hydrochloric acid. Upon potassium hydroxide are dispersed in 150 parts by separation and purification, 51.6 parts by weight of weight of N,N-dimethylformamide and heated to 75C. product are obtained which infrared and gas chromatofor 24 hours. After acidification and the addition of 75 graphic analysis confirm to be the desired a(2 proparts by weight of water and 75 parts by weight petropionylethyl) C C H nitroparaffin product. leurn ether two phases separate. The organic phase is separated, dried and volatiles stripped off. A yield of EXAMPLES 5 To 7 approximately parts by weight of a product that ele- Preparation of Three Other Beta Substituted C C mental infrared and gas chromatography analysis con- Secondary Nitroparaffin Products firm to be beta-(2-carbonylmethoxyethyl) nitrododec- Using the procedure of Example 1 two separate reacam Is Obtamed ti on mixturels arctle heated for 30 hours at C. with st ir- 5O EXAMPLES 10 TO 30 g zi g g g ggi Si hydrochloric acld Preparation of Other Michael-Type Addition Products The first reaction mixture comprised 22 parts by In these examples the procedure described in Examweight of C -C H secondary nitroparaffins, 15 parts by ple l is followed from reaction through isolation. In all weight of phenyl vinyl ketone, 5 parts by weight of instances, parts and percentages are by weight. The powdered potassium hydroxide and 200 parts by 55 summary of these examples appear in Table l which folweight of N, N-dimethylformamide to produce a-(Z- low: benzoylethyl) C -C H nitroparaffin product.

TABLE I Strongly Alkaline REACTANTS PARTS BY WEIGHT Material Parts '7: EXAMPLE Nitroparaffin Vinyl-type Compounds SOLVENT-Parts by Wt. By Weight Yield Mixture Secondary Potassium l0 C,(,CH Nitroparaffin Methyl Vinyl Ketone N.N-dimethylfo rmamidc Hydroxide l 10 parts 45 parts 200 parts l.O parts 64.571

Potassium l l C -C Nitroparaffin 2-Vinyl Pyridine N.N-dimcthylformamide Hydroxide 22 parts 10 5 parts lOO parts l.0 parts 57.3% Potassium 88.4%

TABLE I-continued Strongly Alkaline REACTANTS PARTS BY WEIGHT Material Parts 7! EXAMPLE Nitroparaftin Vinyl-typc Compounds SOLVENT-Parts by Wt, By Weight Yield 12 -C Nitroparaffin Divinyl Sulfone N.N-dimethyltormamide Hydroxide of BIS 168 parts 51 parts 175 parts 1.5 parts Adduct Dimethylamino- Potassium l3 C .,C Nitroparaffin ethyl acrylatc N.N-dimethylformamide Hydroxide 53 parts 42 parts 150 parts 1.5 parts 97.0%

Potassium l4 ln C Nitroparaffin Allyl acrylatc N.N-dimcthylformamide Hydroxide 51 parts 33 parts 150 parts 15 parts 98.071 Ethylene Potassium Mono 15 C .,C H Nitroparaffin Diacrylate N.N-dimethylformamide Hydroxide Adduct 66 parts 52 parts 250 parts 1.5 parts 85.09?

Potassium 16 (S -C Nitroparaffin Hexyl acrylate N.N-dimethylformamide Hydroxide 44 parts 32 parts 150 parts 1.5 parts 94.241

Potassium 17 Z-Nitropropane Methyl acrylate N.N-dimethyltormamide Hydroxide 89 parts 90 parts 150 parts 1.0 parts 989% Mixture Secondary Potassium l8 C -C Nitroparaffins Furfuryl aerylatc N.N-dimethylformamide Hydroxide 110 parts 84 parts 250 parts 3.5 parts 95.8%

' Potassium 19 CHI-CH Nitroparaffins Methallyl acrylatc N.N-dimethyltormamide Hydroxide 108 parts 75 parts 200 parts 1.0 parts Ni-1Q Diethylamine Potassium 20 CmC,. Nitroparaftins aerylatc N.N-dimethylfornutmidc Hydroxide l 15 parts lOO parts -3()() parts 2.0 parts 68.1% Mixture Secondary N.N-dimethylfornwmide Sodium 21 -C Nitroparaffin Phenyl acrylate Hydroxide 108 parts 82.0 parts 250 parts 21 parts 95.091

Potassium Z2 -C Nitroparaffin Butyl acrylate N.N-dimethylt'ormamide Hydroxide 44 parts 29 parts 150 parts S parts 97.8%

Potassium Z3 Cal-C Nitroparaffin Lauryl acrylute N.N-dimethylformamide Hydroxide 45 parts 51 parts 200 parts 5 parts 77.09;

Z-Ethylhexyl Potassium 24 Cat-C Nitroparaffin acrylate N.N-dimethylformamidc Hydroxide 44 parts 41 parts 200 parts 10 parts 91.0;

Cyclohexyl Potassium 25 Car-C Nitroparaffin acrylate NN dimethyltormumide Hydroxide 44 parts 31 parts 200 parts 4 parts 95.4;

Potassium "6 Cub CH Nitroparaft'in Crotononitrile N.N-dimethyltormamide Hydroxide 44 parts 13 parts 100 parts 1 part 30.4";

Potassium 27 -C Nitroparaffin Mcthacrylonitrile N N-dimethylformamide Hydroxide 44 parts 13 parts 100 parts 2 parts 1 1 1" Potassium 28 m'C Nitroparaffin Acrylonitrilc Dimethyl sulfoxide Hydroxide 44 parts 6.5 parts 50 parts 2 parts Hexamethyl Potassium 29 Cur-C Nitroparaffin Crotononitrile Phosphoramide Hydroxide 44 parts 15 parts 50 parts 2 parts 10.4 1

Potassium 30 Cat-C Nitroparaffin Methyl aerylute N N-dimethylformamide Hydroxide Above 44 parts 5 parts 90 "/1 infrared analysis establishes the expected product forms. Run in autoclave under autogenous pressure,

TABLE II Vinyl- Exam- Type plc Nitroparaffin Reaetant Product 55. 3| scc.nitrodecane acrylo- /3-( Z-cyanoethyl) nitrile nitrodecane EXAMPLES 3] TO 44 32 Seonitrodecane mcthallyl B-(2-carhonyllzt th'll ."th'l) Preparation of Individual Michael-Type Adducts of C gggj to C Nitroparaffins with Vinyl-Type Reactant 33 ni roun n acrylofi-(Z-cyunoethyl) nitrilc nitroundecane In these runs specific C -C nttroparaffins are re- 60 3 seenitroundccunc methullyl B-(3-carbonylacted with designated reactant on a 1:2 molar basis in 21 N,Ndimethylformamide solvent environment 35 sectnitrododccanc acry1o- B-( Z-cyanoethyl) (100ml) at 75C. in the presence of 2% by wt. KOH "mile itfododcclmc 36 sec.nltrododecane methallyl ,B( Z-carbonyl- (based on nttroparaffin content) usmg the procedure 86mm mcthunvloxvethvl) described in Example 1. In each instance yields of ,5 37 v nitrododecanc I r w or more are obtained of the Indicated beta-substituted sec'mtmmdecdnc gf gf gr ethylated product as confirmed by infrared, gas chro- 38 seenitrotridccunc ethullyl B-(Z-carbonylmatography and nuclear magnetic resonance data. The i l fg g'lg l n CCLH'IC res are shown In the table o 39 seenitrotctradccanc aerylo- B-(Z-cyanoethyl) o 7 TABLE commued The molding is doneat 350 F. pith a pressure of -5 tons, and a molding time of 8 minutes. Em l Table III which follows summarizes the physical chare ple Nitroparaffin ac l m product acteristics of polyvinyl chloride polymers plasticized 5 with various adducts of the invention when evaluated nitrile nitrotetradccanc 4 .1 swninmctmdccunc according to standard testing procedures. 4] d "E I f g p As a basis for making an evaluation of the invention sec.nitrotetra ecane met ya y -car on I I ucrylmc nmhuuylnxwhm adducts as plasticizers, the same. polyvinyl chloride pol iiitrotetradecane ymer and antioxidant are blended in the same propor- 3 H s s 0 m 10 tion with a commercially employed plasticizer diisoocnirmm'mlibcmlc tyl phthalate and also with a mixture of C ,.,C nitro- 43 paraffins. All of the materials are milled and molded acrylate methoxvethvl) nitmdcdn'c under identical conditions and temperatures to pro- 44 seciiiitrododecane metlhyl B-(Z-carhonylduce the polymer compositions. The results obtained acr) ate methoxyethyll 3 nhmdodwmc when this composition is exposed to the same tests are also given in Table III.

TABLE III 71 Clash Tensile Extrn 71 Berg Mod. psi Tensile Shore /l With Extm. Temp. at COMPOUNDS at I009} Mod. psi Hardness Elong. Soap With Carbon G=45UUO Ex EVALUATED Elong. at Break A at Break Water Hexanc Volatility psi 45 Disooctyl Phthalate I-lUll 2880 84.2 360 5.2 21.0 1.5 I6 46 (Cm-C Nitroparal'fin Mixture I350 2970 83.9 350 I21) l I.() 14.0 23 47 Adduei 01 Ex. I 1147 2906 x04 410 10.0 3.7 7.4 21 4x Adtluct 01 Ex. 3 11:7 2788 78.7 382 11.2 11.5 8.6 I8 49 Adduct 01 Ex. is 1224 21400 82.6 420 6.8 23.2 2.9 23 50 Adduet of Ex. 6 1071 21473 77.8 382 10.7 7.7 11.21 17 51 Adduct 01' 20 1570 2959 390 52 Adduct of Ex. 21 1750 3179 336 3.6 10.0 1.3 4 53 Adduct of 1:78 3005 84.3 420 10.9 14.4 7.9 21.5 54 Adduct ofEx. 12 1474 2912 87.3 397 34.6 22.7 2.3 55 Adduet 01 Ex. 14 1715 3154 89.0 360 7.5 4.4 2.0 7 5e Adduct Uri-ix. 15 1300 2711 84.0 330 5.7 12.3 4.0 19 57 Adtluct 01 Ex. 17 1703 3317 85.4 347 6.5 3.2 2.0 0

As the numerous examples andsuggested embodiments indicate. this invention is advantageous in several respects. For example, the inventive process is advantageous in that it permits the use of secondary nitro- EXAMPLES 45 TO 49 paraffins containing 10 and higher carbon atoms as reactants in Michael-type additions without adversely af- Evaluation 0 'v Adducts Pre i g g fizg g i li f f fecting yields. In addition, these nitroparaffin reactants Com oungs as Plasti i s r P ii g? T can be in the form of the solvent-free individual comp S fi o 3 my on 6 pounds of their mixtures, or the nitroparaffin reactants y e can contain a large quantity of inert solvent such as the In these examples the designated adducts are formuparaffins. Further, the good yield of addition products lated with polyvinyl chloride and an antioxidant using is obtained within short reaction times without the use the procedure described below: of pressurized systems at relatively low reaction tem- A parts by weight portion of the adduct being peratures. evaluated as plasticizers is blended with 1.5 parts by In its product aspect this invention provides heretoweight of antioxidant (Thermolite 3l and 100 parts by 50 fore unknown adducts of C and higher nitroparaffins weight portion of commercially obtained polyvinyl chloride is blended into the mixture. The polymer blend is slowly added to the mill rolls of a mill whose roller speed is maintained at 20 feet per minute at 350F. and whose back roller temperature is maintained at 375F. After all of the polymer blend is added to the rollers (usually 3-4 minutes) the mixing is continued on the rollers. After each milling run, the milled polymer is removed and the milling process is repeated 4 to 6 times for a total of l2-I6 minutes. At this time the blended and milled polymer is removed and molded using two molds both 8 /2 inches X 10 inches and having a capacity of 10 ml. and the second a 75 ml. capacity.

with vinyl-type materials. These products are useful generally as bifunctional intermediates and as plasticizers for polyvinyl polymers.

The preceding specification demonstrates that numerous changes, modifications and substitutions can be made in the practice of this invention without departing from the inventiveconcept. The metes and the bounds of this invention can be determined by the claims which follow read in conjunction with the specification.

What is claimed is:

1. ,8-(2-carbonylmethoxyethyl) secondary Clo-C nitroparaffins.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION Q PATENT NO. 3,923,846 I DATED DECEMBER 2, 1975 |NVENTOR(5 WHEELER c. CRAWFORD; WILLIAM P.DOYLE;JOHN A.PATTERSON It is certified that error appears in the above-identified patent and that said Letters Patent O are hereby corrected as shown below:

INVENTOR'S NAME WHELLER C. CRAWFORD SHOULD READ --WHEELER C. CRAWFORD-- COL. 1, line 60, "vinyl-tape" should read vinyltype- COL, 8, TABLE I, last line under- Yield, "88. 4% should be deleted COL. 9, EXAMPLE 12, last line under Yield, insert 88.4%

6 COL. 9, EXAMPLE 17, first column under "Nitroparaffin" delete "Mixture Secondary" and insert "Mixture Secondary" on next line, as part of Example 18.

2 En'gned and Scaled this thirteenth Day Of April1976 [SEAL] Arrest: i

i RUTH C. MASON C. MARSHALL DANN Arresting ()jj'r'rer (mnmissimn'r uflarems and Trademarks lmmwhgl.

'UNITED STATES PATENT AND TRADEMARK OFFICE R CERTIFICATE OF CORRECTION PATENT N0.\ 3 ,923, 846 DATED December 2 1975 V 1 Wheeler C. Crawford, William P.Doyle, John A It IS certlfled that error appears In the above-ldentlfled patent and that said Letters SzJIenI are hereby corrected as shown below:

The inventor's name "WHELLER C. CRAWFORD" should read -WHEELER C. CRAWFORD-- Col. 1, line 60, "vinyl-tape" should read --vinyl-type-- Col. 8, Table I last column under Example 11,

"88. 4%" should appear under Example 12, last column.

Col. 9, Table I, "Mixture Secondary" should be moved one space to be part of Example 18.

Signed and Scaled this A ttest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner oj'Patenls and Trademarks 

1. B:(2-CARBONYLMETHOXYETHYL) SECONDARY C10-C14 NITROPARAFFINS. 